CN101254468A - Nano load phosphotungstic acid catalyst and method of preparing the same - Google Patents
Nano load phosphotungstic acid catalyst and method of preparing the same Download PDFInfo
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- CN101254468A CN101254468A CNA2008100546725A CN200810054672A CN101254468A CN 101254468 A CN101254468 A CN 101254468A CN A2008100546725 A CNA2008100546725 A CN A2008100546725A CN 200810054672 A CN200810054672 A CN 200810054672A CN 101254468 A CN101254468 A CN 101254468A
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- phosphotungstic acid
- catalyst
- acid catalyst
- zirconyl nitrate
- nano load
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a nano-sized supported phosphotungstic acid catalyst which has a structural formula as follows: PW-ZrO2-SiO2. The catalyst is prepared by the following steps: pre-hydrolyzing tetraethoxysilane and zirconyl nitrate as raw materials in an aqueous solution of ethanol, adding phosphotungstic acid, heating gradually up to 60-100 DEG C to form a gel, vacuum-drying, calcining at 300-500 DEG C for 3-6 hours to obtain PW-ZrO2-SiO2. The prepared PW-ZrO2-SiO2 has high catalytic activity, good stability and easy product separation. The catalyst can be used in catalytic reaction of acids, as well as catalytic esterification of polyalcohols.
Description
Technical field
The present invention relates to a kind of nanocatalyst, specifically belong to a kind of nano load phosphotungstic acid catalyst and preparation method thereof.
Background technology
The polyester of polyalcohol and dicarboxylic acid polyester reaction (unary fatty acid is made end-capping reagent) preparation has purposes widely, for example can be used for alkyd resins, coating, lubricating oil and plasticizer.But traditional esterification adopts inorganic acid such as the concentrated sulfuric acid to carry out catalysis, and not only severe reaction conditions (generally require high temperature, vacuumize), slow, the consuming time length of reaction rate, efficient are low, and produce a large amount of three wastes, and environment is caused severe contamination.Therefore, research can reduce reaction temperature, shortening reaction time, reduce the green catalyst of three-waste pollution, seems particularly important.
Phosphotungstic acid (the Phosphotungstic acid of Keggin type structure, be abbreviated as PW) as a kind of eco-friendly heterogeneous catalyst, obtained in recent years using widely, this all has superpower acidity, high thermal stability and lower advantages such as oxidation potential owing to it.Because the very little (＜10m of specific area of phosphotungstic acid
2/ g), very easily water-soluble and polar solvent makes pure phosphotungstic acid use as catalyst and is very limited.Carrier commonly used has silica, active carbon, molecular sieve etc.V.M.Mastikhin etc. pass through
1H MAS NMR and
31P NMR measures discovery, and after phosphotungstic acid loaded on silica surface, because the strong interaction between carrier and the catalyst molecule, its Keggin type structure changed to some extent, causes catalytic activity to reduce.
Summary of the invention
The purpose of this invention is to provide nano load phosphotungstic acid catalyst of a kind of catalytic activity height, good stability and preparation method thereof.
A kind of nano load phosphotungstic acid catalyst provided by the invention, structural formula is: PW-ZrO
2-SiO
2
The preparation method of a kind of nano load phosphotungstic acid catalyst provided by the invention specifically comprises the steps:
(1) zirconyl nitrate is added in the deionized water, normal temperature stirs down, dissolving, and zirconyl nitrate and water mol ratio are 1: 20～100; Be 1: 1～9 to get in the ethyl orthosilicate adding absolute ethyl alcohol in addition, mix under the normal temperature that the mol ratio of ethyl orthosilicate and absolute ethyl alcohol is 1: 2～10 according to the mol ratio of zirconyl nitrate and ethyl orthosilicate;
(2) above-mentioned solution is mixed, under 20～50 ℃ condition, stir prehydrolysis 1～2 hour;
(3) phosphotungstic acid of getting zirconyl nitrate and ethyl orthosilicate gross mass 5～20% adds in the above-mentioned mixed solution, and solution becomes when transparent, continues heating, temperature reaches 60～100 ℃, and constant temperature 0.5～2 hour is when obtaining flaxen clear gel, stop to stir cooling and aging 1～2 day;
(4) with the gel after the ageing 60～100 ℃ of following vacuum drying 3～5 hours, obtain xerogel;
(5) with above-mentioned xerogel 300～500 ℃ of following roastings 3～6 hours, obtain catalyst P W-ZrO
2-SiO
2
PW-ZrO
2-SiO
2Can in general acid catalyzed reaction, use, particularly the application in the polyesterification reaction of polyalcohol (neopentyl glycol, trimethylolpropane or pentaerythrite) and binary acid (adipic acid, azelaic acid or certain herbaceous plants with big flowers diacid) (unary fatty acid (enanthic acid, sad, n-nonanoic acid or certain herbaceous plants with big flowers acid) is made end-capping reagent) process.
Advantage compared with prior art of the present invention and effect: (1) composite oxide carrier ZrO
2-SiO
2Middle ZrO
2Existence, improved active component and carrier interactions, significantly improved activity of such catalysts; (2) adopted sol-gel process to prepare catalyst, preparation technology is simple, and reaction time is short, and technological parameter is easy to control, and the active component high degree of dispersion is in carrier composite oxides ZrO
2-SiO
2Network structure in, not only kept advantages of high catalytic activity, and good stability, active component is difficult for stripping, and is easy to be recycled; (3) nanocatalyst after the load easily separates with the polyphosphazene polymer ester products, and post processing is simple, has simplified polyesterification technology, has improved the purity and the stability of polyester product; (4) use of this catalyst not only makes the polyesterification reaction condition become gentle, and reaction temperature reduces, and the reaction time shortens, and because catalyst can reclaim repeated use, environment is not produced any pollution.
Description of drawings
Fig. 1 nanocatalyst that to be method for preparing catalyst provided by the invention make by embodiment 1,2,3 and the solid violet external reflectance spectrogram (UV-VIS) of pure PW and pure carrier.Obviously, among the figure pure phosphotungstic acid 254 and the peak at 400nm place very big variation has taken place in supported catalyst, illustrate that PW is scattered in the zirconium silicon composite oxide carrier fully.
Fig. 2 is method for preparing catalyst provided by the invention makes nanocatalyst PW-30Z-70S by embodiment 2 a transmission electron microscope picture.As seen from the figure, mostly to be diameter be microballoon about 200nm to product.
The specific embodiment
Embodiment 1
Take by weighing the 1.12g zirconyl nitrate, add the 20.3ml deionized water, stirring and dissolving under the normal temperature; Other measures the 8.5ml ethyl orthosilicate, adds the stirring under 20 ℃ of 13ml absolute ethyl alcohol and carries out prehydrolysis.When treating that above-mentioned two solution all become limpid, two solution are mixed, and under 40 ℃ condition, continue prehydrolysis 1 hour.In above-mentioned mixed liquor, add the 1.2g phosphotungstic acid, be heated to 80 ℃ after, constant temperature 1 hour obtains flaxen clear gel, stops to stir, and changes the beaker cooling and aging over to 24 hours.Gel after the ageing is put into vacuum drying chamber, and 80 ℃ of temperature controls dry 5 hours down obtain xerogel, at last with xerogel 450 ℃ of following roastings 4 hours, obtain containing the PW-10ZrO of 30% phosphotungstic acid
2-90SiO
2The nano load catalyst.
Embodiment 2
Take by weighing the 2.84g zirconyl nitrate, add the 14ml deionized water, normal temperature stirs down and makes dissolving; Other measures the 5.5ml ethyl orthosilicate, adds the stirring under 20 ℃ of 8.4ml absolute ethyl alcohol and carries out prehydrolysis.When treating that above-mentioned two solution all become limpid, two solution are mixed, and under 40 ℃ condition, continue prehydrolysis 1 hour.In above-mentioned mixed liquor, add the 1.2g phosphotungstic acid, be heated to 80 ℃ after, constant temperature 1 hour obtains flaxen clear gel, stops to stir, and changes the beaker cooling and aging over to 24 hours.Gel after the ageing is put into vacuum drying chamber, and 80 ℃ of temperature controls dry 5 hours down obtain xerogel, at last with xerogel 450 ℃ of following roastings 4 hours, obtain containing the PW-30ZrO of 30% phosphotungstic acid
2-70SiO
2The nano load catalyst.
Embodiment 3
Take by weighing the 4.08g zirconyl nitrate, add the 20ml deionized water, normal temperature stirs down and makes dissolving; Other measures the 3.4ml ethyl orthosilicate, adds the stirring under 20 ℃ of 5.2ml absolute ethyl alcohol and carries out prehydrolysis.When treating that above-mentioned two solution all become limpid, two solution are mixed, and under 40 ℃ condition, continue prehydrolysis 1 hour.In above-mentioned mixed liquor, add the 1.2g phosphotungstic acid, be heated to 80 ℃ after, constant temperature 1 hour obtains flaxen clear gel, stops to stir, and changes the beaker cooling and aging over to 24 hours.Gel after the ageing is put into vacuum drying chamber, and 80 ℃ of temperature controls dry 5 hours down obtain xerogel, at last with xerogel 450 ℃ of following roastings 4 hours, obtain containing the PW-50ZrO of 30% phosphotungstic acid
2-50SiO
2The nano load catalyst.
Table 1, PW-ZrO
2-SiO
2Catalyst elements content data table (ICP-AES)
Table 1 nanocatalyst that to be method for preparing catalyst provided by the invention make by embodiment 1,2,3 and the constituent content tables of data (ICP-AES) of pure PW and pure carrier.As can be known from the table data, according to the catalyst that the invention provides the method preparation, through after the high-temperature roasting, PW stably is distributed on the carrier, the content of zirconium, silicon and PW and rate of charge basically identical in the carrier.
Embodiment 4 PW-ZrO
2-SiO
2Application of Catalyst
In the 250ml there-necked flask of condenser pipe, thermometer, water knockout drum is housed, add the PW-ZrO that 13.5g trimethylolpropane, 14.6g adipic acid, 0.2g such as embodiment 2 obtain
2-SiO
2With 100ml dimethylbenzene, be heated to 140 ℃, behind the back flow reaction 1.5h, add the 22ml enanthic acid, after continuing to react 5h, cessation reaction.Remove by filter catalyst while hot, adopt rotary evaporation to remove solvent after, slough low-molecular-weight not polymerizate with distillation under vacuum, obtain productive rate and be 95% mean molecule quantity and be distributed in the poly-dihydroxymethyl butanols of adipic acid between the 700-4000.
Claims (4)
1. a nano load phosphotungstic acid catalyst is characterized in that structural formula is: PW-ZrO
2-SiO
2
2. according to the preparation method of the described a kind of nano load phosphotungstic acid catalyst of claim 1, it is characterized in that comprising the steps:
(1) zirconyl nitrate is added in the deionized water, normal temperature stirs down, dissolving, and zirconyl nitrate and water mol ratio are 1: 20～100; Be 1: 1～9 to get in the ethyl orthosilicate adding absolute ethyl alcohol in addition, mix under the normal temperature that the mol ratio of ethyl orthosilicate and absolute ethyl alcohol is 1: 2～10 according to the mol ratio of zirconyl nitrate and ethyl orthosilicate;
(2) above-mentioned solution is mixed, under 20～50 ℃ condition, stir prehydrolysis 1～2 hour;
(3) phosphotungstic acid of getting zirconyl nitrate and ethyl orthosilicate gross mass 5～20% adds in the above-mentioned mixed solution, and solution becomes when transparent, continues heating, temperature reaches 60～100 ℃, and constant temperature 0.5～2 hour is when obtaining flaxen clear gel, stop to stir cooling and aging 1～2 day;
(4) with the gel after the ageing 60～100 ℃ of following vacuum drying 3～5 hours, obtain xerogel;
(5) with above-mentioned xerogel 300～500 ℃ of following roastings 3～6 hours, obtain catalyst P W-ZrO
2-SiO
2
3, according to the application of the described a kind of nano load phosphotungstic acid catalyst of claim 1 in acid catalyzed reaction.
4, according to the application of the described a kind of nano load phosphotungstic acid catalyst of claim 3 in the polyol polyester catalytic reaction.
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| CNA2008100546725A CN101254468A (en) | 2008-03-20 | 2008-03-20 | Nano load phosphotungstic acid catalyst and method of preparing the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102791372A (en) * | 2010-03-17 | 2012-11-21 | 出光兴产株式会社 | Catalyst for oligomerization of olefins |
| CN107163233A (en) * | 2017-05-19 | 2017-09-15 | 浙江帝恒实业有限公司 | A kind of plasticizer and preparation method thereof |
| CN108147797A (en) * | 2018-01-04 | 2018-06-12 | 中国人民解放军国防科技大学 | Three-dimensional carbon fiber reinforced silica-zirconia composite ceramic material and preparation method thereof |
| CN112940230A (en) * | 2021-02-03 | 2021-06-11 | 湖南工学院 | Alkyd resin and preparation method thereof |
-
2008
- 2008-03-20 CN CNA2008100546725A patent/CN101254468A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102791372A (en) * | 2010-03-17 | 2012-11-21 | 出光兴产株式会社 | Catalyst for oligomerization of olefins |
| CN107163233A (en) * | 2017-05-19 | 2017-09-15 | 浙江帝恒实业有限公司 | A kind of plasticizer and preparation method thereof |
| CN108147797A (en) * | 2018-01-04 | 2018-06-12 | 中国人民解放军国防科技大学 | Three-dimensional carbon fiber reinforced silica-zirconia composite ceramic material and preparation method thereof |
| CN108147797B (en) * | 2018-01-04 | 2020-12-04 | 中国人民解放军国防科技大学 | Three-dimensional carbon fiber reinforced silica-zirconia composite ceramic material and preparation method thereof |
| CN112940230A (en) * | 2021-02-03 | 2021-06-11 | 湖南工学院 | Alkyd resin and preparation method thereof |
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Open date: 20080903 |